Subscriber access provided by UNIVERSITY OF ADELAIDE LIBRARIES
Article
High quantities of microplastic in Arctic deepsea sediments from the HAUSGARTEN observatory Melanie Bergmann, Vanessa Wirzberger, Thomas Krumpen, Claudia Lorenz, Sebastian Primpke, Mine B. Tekman, and Gunnar Gerdts Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.7b03331 • Publication Date (Web): 17 Aug 2017 Downloaded from http://pubs.acs.org on August 22, 2017
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Environmental Science & Technology is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
Page 1 of 34
Environmental Science & Technology
1
High quantities of microplastic in Arctic deep-sea
2
sediments from the HAUSGARTEN observatory
3 4
Melanie Bergmann†,ǁ,*, Vanessa Wirzberger‡,§,ǁ, Thomas Krumpen⊥, Claudia Lorenz‡, Sebastian
5
Primpke‡, Mine B. Tekman†, Gunnar Gerdts‡
6 7
†
8
Zentrum für Polar- und Meeresforschung, Am Handelshafen 12, 27570 Bremerhaven, Germany
9
*Corresponding author. E-Mail:
[email protected] HGF-MPG Group for Deep-Sea Ecology and Technology, Alfred-Wegener-Institut Helmholtz-
10
‡
11
Helmholtz-Zentrum für Polar- und Meeresforschung, Kurpromenade, 27498 Helgoland,
12
Germany
13
§
14
Chemistry, Universitätsstrasse 5, 45141 Essen, Germany
15
⊥Climate
16
Meeresforschung, Bussestraße 24, 27570 Bremerhaven, Germany
17
ǁ
Department of Microbial Ecology, Biologische Anstalt Helgoland, Alfred-Wegener-Institut
University Duisburg-Essen, Faculty of Chemistry, Department of Instrumental Analytical
Sciences, Sea Ice Physics, Alfred-Wegener-Institut Helmholtz-Zentrum für Polar- und
Shared first authors
18
1 ACS Paragon Plus Environment
Environmental Science & Technology
19
ABSTRACT:
20
Although mounting evidence suggests the ubiquity of microplastic in aquatic ecosystems
21
worldwide, our knowledge of its distribution in remote environments such as Polar Regions and
22
the deep sea is scarce. Here, we analyzed nine sediment samples taken at the HAUSGARTEN
23
observatory in the Arctic at 2,340 – 5,570 m depth. Density separation by MicroPlastic Sediment
24
Separator and treatment with Fenton’s reagent enabled analysis via Attenuated Total Reflection
25
FTIR and µFTIR spectroscopy.
26
Our analyses indicate the wide spread of high numbers of microplastics (42 – 6,595
27
microplastics kg-1). The northernmost stations harbored the highest quantities, indicating sea ice
28
as a transport vehicle. A positive correlation between microplastic abundance and chlorophyll a
29
content suggests vertical export via incorporation in sinking (ice-) algal aggregates. Overall, 18
30
different polymers were detected. Chlorinated polyethylene accounted for the largest proportion
31
(38 %), followed by polyamide (22 %) and polypropylene (16 %). Almost 80 % of the
32
microplastics were ≤ 25 µm.
33
The microplastic quantities are amongst the highest recorded from benthic sediments, which
34
corroborates the deep sea as a major sink for microplastics and the presence of accumulation
35
areas in this remote part of the world, fed by plastics transported to the North via the
36
Thermohaline Circulation.
2 ACS Paragon Plus Environment
Page 2 of 34
Page 3 of 34
37
Environmental Science & Technology
INTRODUCTION
38
The contamination of our oceans with plastic debris is a problem of growing
39
environmental concern. Recently, it was estimated that 8,300 million metric tons (MT) of plastics
40
have been produced to date, 6,300 MT of which have become waste as of 2015.1 Between 4.8
41
and 12.7 million MT of plastic debris entered the ocean from land in 2010.2 However, 99 % of
42
this debris have not been captured by global litter estimates.3 It has been speculated that a large
43
fraction of plastic debris may escape our sampling gears because of uptake and transport by
44
biota, accumulation on the largely inaccessible deep seafloor and in other remote environments
45
or by fragmentation into smaller particle sizes. In the marine realm, the integrity of plastics is
46
compromised through mechanic abrasion, interaction with biota, UV radiation and temperature
47
fluctuations such that it brittles and fragments.4 Particles smaller than 5 mm are considered
48
microplastics (MPs).5 Sources for plastic in the oceans can be anthropogenic waste, which is
49
dumped directly into the sea by fishers and other ships, aqua culture, ship yards, beach visitors,
50
daily care products and washed out fibres from synthetic textiles. Municipal drainage systems,
51
road runoff and rivers represent additional entry points.6
52
Although MPs were discovered as early as in the 1970’s
7
the scientific research
53
intensified only after time-series data highlighted increasing MP contamination of Atlantic waters
54
and MP ingestion by marine biota.8 Since then, MP has been identified in all marine realms from
55
beaches to the deep seafloor and in all oceans and seas worldwide.9, 10 Plastic in this size range
56
is of particular concern because it can be taken up by a wider range of biota (>172 species) and
57
be propagated in food webs.9 While some organisms excrete MP without any apparent effect,11
58
in others ingested MP may interfere with food uptake and transfer adsorbed and added toxins.9
59
In addition, MP between 0.5 and 438 µm may translocate to organs or blood
60
effects. Despite increased research efforts, however, the overall ecological consequences of
61
MPs are still not clear.
3 ACS Paragon Plus Environment
12-14
amongst other
Environmental Science & Technology
Page 4 of 34
62
The discovery of oceanic gyre-associated accumulation zones, so called ‘garbage
63
patches’,15 also stimulated intensified research efforts. Five such systems were confirmed to
64
date and the suspected presence of further accumulation zones in the Arctic
65
corroborated.17 Cózar et al. reported increasing plastic concentrations towards the northernmost
66
borders of the Greenland Sea due to the barrier imposed by the ice sheet.17 One of these zones
67
west of Svalbard happens to be close to the HAUSGARTEN observatory, from which increasing
68
litter quantities were recorded on the deep seafloor between 2002 and 2014.18, 19 Litter and MP
69
were also recorded from the nearby sea surface.20,
70
quantities of MPs (Peeken, unpubl. data).22 Tekman et al. reported increasing numbers of
71
smaller-sized plastic items (< 10 cm) on the deep seafloor.19 Although the deep seafloor may
72
constitute a major sink for MP until now only three studies were dedicated to MP in deep-sea
73
sediments at depths between 1,000 – 5,800 m from the Nile Deep Sea Fan, Southern Ocean,
74
Porcupine Abyssal Plain, Mediterranean Sea, SW Indian Ocean, NE Atlantic Ocean and the NW
75
Pacific Kuril-Kamchatka Trench.23-25
21
16
was recently
In addition, Arctic sea ice contains vast
76
The aim of this study is to quantify MP pollution on the Arctic seafloor in the
77
HAUSGARTEN observatory along a bathymetric transect ranging from 2,500 - 5,500 m depth.
78
Sediments taken along a latitudinal gradient were also analyzed to assess the importance of MP
79
release due to melting processes in the marginal ice zone. To attempt source allocation, the
80
polymer composition of all particles identified is described and compared. In the absence of a
81
standard operation procedure for the analysis of MP from sediments,5 a new method was
82
adopted to remove organic material (Fenton’s reagent) prior to analysis by Fourier-transform
83
infrared (FTIR) spectroscopy.26
84
4 ACS Paragon Plus Environment
Page 5 of 34
85
Environmental Science & Technology
MATERIALS AND METHODS
86
Study area. The sediments analyzed during this study were taken from the Long-Term
87
Ecological Research (LTER) observatory HAUSGARTEN in the summer of 2015 during
88
expedition ARK 29.2 of the research icebreaker RV Polarstern. HAUSGARTEN was established
89
by the Alfred Wegener Institute Helmholtz Centre for Polar and Marine Research in 1999 in the
90
Fram Strait at N79°, west of Svalbard (Norway). It currently comprises 21 sampling stations
91
along a latitudinal and a bathymetric gradient between 250 – 5,500 m water depth.27 These
92
stations are subject to annual sampling campaigns targeting all ecosystem compartments from
93
the sea surface to the deep seafloor. The Fram Strait represents the only deep-water connection
94
between the North Atlantic and the Arctic Ocean. The HAUSGARTEN area is affected by warm
95
Atlantic waters transported by the West Spitsbergen Current in the upper 500 m, which is fed by
96
the north Atlantic waters, such that the area is ice-free for most of the year. Still, the northern
97
HAUSGARTEN stations N3 and N5 are covered by ice during winter, but ice can also be present
98
during summer when it is carried from the Central Arctic into the Fram Strait by the Transpolar
99
Drift.19 Below the warm Atlantic water layer, there are low-temperature waters modified by polar
100
water masses.28
101
Sediment sampling. To obtain virtually undisturbed sediment samples, a video-guided
102
multiple corer (MUC; Oktopus GmbH) holding eight cores of 100 mm diameter was used. Three
103
stations were sampled along the latitudinal gradient (N5, N3, S3), which runs along the 2,500 m
104
isobath (Table 1, Figure 1). These include the northernmost station N5, which is located in the
105
marginal ice zone. Six samples were taken at stations from the bathymetric gradient (HG-IV –
106
IX: 2,342 – 5,570 m water depth), including the Molloy Deep, the deepest part of the Arctic
107
Ocean (Table 1, Figure 1). Depending on availability, the top 5 cm of 3 – 6 sediment cores were
108
sliced off with a metal spatula and frozen in tin foil. Three additional samples were taken from
109
different MUC cores with cut-off syringes and analyzed at 1-cm intervals down to 5 cm sediment
110
depth. The bulk pigments registered by this method are termed chloroplastic pigment 5 ACS Paragon Plus Environment
Environmental Science & Technology
Page 6 of 34
111
equivalents and indicate phytodetrital input to the seafloor.29 They were extracted in 90%
112
acetone and measured with a Turner fluorometer.30, 31
113
In the laboratory, frozen sediments from all the cores of each station were defrosted,
114
pooled and homogenized. Before the separation, the dry weight was determined by weighing
115
three
sub-samples
from
each
sample
before
and
6 ACS Paragon Plus Environment
after
drying
at
60 °C.
Page 7 of 34
116
Environmental Science & Technology
Table 1. Details of sediment sampling at HAUSGARTEN stations, biogeochemical parameters and prevailing summer sea ice conditions. S3
HG-IV
HG-V
HG-VI
HG-VII
HG-VIII
HG-IX
N3
N5
PS93/48-11
PS93/50-19
PS93/51-4
PS93/53-3
PS93/54-2
PS93/55-2
PS93/56-1
PS93/85-2
PS93/60-10
Date (dd/mm/yy)
25/07/15
27/07/15
28/07/15
28/07/15
29/07/15
29/07/15
29/07/15
11/08/15
03/08/15
Latitude (N)
78°35,98'
79°04,91'
79°03,81'
79°03,61'
79°03,63'
79°3,86'
79°08,02'
79°36,25'
79°56,28'
Longitude (E)
5°04,07'
4°08,59'
3°39,46'
3°34,98'
3°28,56'
3°20,10'
2°50,58'
5°10,28'
3°11,60'
2,342
2,460
3,127
3,430
4,092
5,108
5,570
2,783
2,549
0.00
0.79
0.79
0.79
0.79
2.61
2.61
3.47
35.33
0
2
2
2
2
8
8
13
84
60.54
53.86
51.01
47.26
42.34
36.91
60.72
58.97
60.48
1.25
1.38
1.42
1.30
1.38
1.45
1.11
n.a.
1.33
13.19
15.40
14.73
13.86
14.03
17.53
18.35
n.a.
17.71
0.78
0.66
0.74
0.61
0.59
0.68
1.09
0.88
0.88
4.75
20.53
51.81
16.01
9.63
6.67
10.22
33.76
8.53
Sampling cast
Depth (m) Mean ice concentration (%) Duration of ice coverage (days) Porosity (%) Chlorophyll a (µg cm-3) Chloroplastic pigment equivalent (µg cm-3) Particulate organic carbon (%) -1
Phospholipids (nmol ml )
7
ACS Paragon Plus Environment
Environmental Science & Technology
117
Sediment characterization and separation. The MicroPlastic Sediment Separator
118
(MPSS; HYDRO-BIOS GmbH) was used to separate the denser sediment particles from the
119
less dense MP particles.32 A ZnCl2 solution (1.7 – 1.8 g cm-3 density) was filtered into the
120
MPSS using cartridge filters (10-µm stainless steel and 1-µm pleated PP; Wolftechnik
121
Filtersysteme GmbH & Co. KG) each time prior to the addition of sediments. A steel rotor on
122
the bottom of the MPSS mixed the sediment at ~12 rpm for 35 – 60 min. The MPSS was
123
filled to the lower half of the dividing chamber after the rotor had been turned off to avoid
124
overflow of the sample. After 12 h, the MPSS was filled up to the upper part of the dividing
125
chamber and left for 7 h. Finally, the ball valve between the two dividing chambers was
126
closed and the ZnCl2 solution above the ball valve was rinsed with Milli-Q into a glass bottle
127
with glass cap and stored at 4 °C until further analysis.
128
Preparation of the samples prior to analysis. A filtration step was required to
129
remove the ZnCl2 solution and to separate the sample into particle size fractions larger and
130
smaller than 500 µm since µFTIR analysis in transmission mode can only identify particles
500 µm). The large size fraction was sorted using a
138
stereomicroscope (Olympus SZX16) and Bogorov chamber (10.5 × 7.3 cm) before analysis
139
by attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR) of suspect
140
MP particles. Each sample was assessed at 16-fold and some particles even at 32-fold
141
magnification. Generally, particles of clear and homogeneous colouration and without cellular
142
or organic structure were selected for analysis by ATR-FTIR.33 The size of all particles was
143
determined by measuring the longest dimension with the cellSens software (Olympus).
144
Currently, fibers cannot be well discerned by the applied Fourier-transform infrared 8 ACS Paragon Plus Environment
Page 8 of 34
Page 9 of 34
Environmental Science & Technology
145
microscopy (µFTIR) analytical method, which was used for the small size fraction (s. below).
146
Therefore, they were also omitted in the analysis of particles of the large size fraction.
147
Small size fraction (< 500 µm). While previous studies relied on enzymatic
148
digestion, H2O2, acid or alkaline treatments to reduce organic material prior to spectroscopic
149
analysis 34-36 Fenton’s reagent (FeSO4 in combination with H2O2) was recently suggested as a
150
promising alternative agent.26 The small size fraction was thus treated with Fenton’s reagent
151
to remove organic matter prior to µFTIR analysis. Briefly, a 7.2 mM FeSO4 solution (pH 500 µm) using a Tensor 27
163
spectrometer (Bruker Optics GmbH) including a platinum ATR unit (wave number range:
164
400 – 4,000 cm-1, 4 cm-1 resolution, 6 mm aperture, 32 scans). After measurement, the
165
spectrum was compared against reference spectra through a library search with the software
166
Opus 7.5. Particles with a hit quality above 700 (max. of 1,000 hit quality) were accepted as
167
verified polymers. The library is available upon request.
168
The small size fraction (< 500 µm) was measured by a TENSOR 27 spectrometer
169
(Bruker Optics GmbH) connected to a Hyperion 3000 µFTIR microscope equipped with a
170
focal plane array (FPA) detector with 64 × 64 detector elements. An infrared range of 1,250 –
171
3,600 cm-1 was used for measurements. Six scans were performed per field at a resolution of
172
8 cm-1 and a binning factor of 4 (see 37 for setting details). 9 ACS Paragon Plus Environment
Environmental Science & Technology
173
After drying for at least two days (30 °C) the filter was placed under the FTIR-microscope
174
onto a calcium fluoride window and an overview image was recorded. Subsequently, the
175
concentrated filter area (166 mm², 73 × 73 FPA fields, 1.36 million spectra) was measured,
176
which took ca. 13 h.
177
Automated analysis of µFTIR data. The data were processed by automated
178
analyses of µFTIR data.38 Briefly, each spectrum in the measurement file was analyzed via
179
two library searches to confirm polymer identity. The library is available upon request. Each
180
pixel identified was stored with its position, analysis quality and polymer type into a file, which
181
was subject to image analysis based on Python 3.4 scripts and Simple ITK functions.38 This
182
combination enabled the identification, quantification and size determination of all polymer
183
particles in a sample and additionally excluded human bias.38 To reduce the complexity of
184
the size distribution the analysis introduced size classes (for details see 38).
185
Contamination protection. If not stated otherwise all laboratory ware used was
186
made of glass or stainless steel and thoroughly rinsed with Milli-Q before use. All polymer-
187
based items, which could not be replaced by alternative glass items (e.g. bottle caps, filter
188
holders) were made of polytetrafluoroethylene (PTFE). Dustboxes ® (DB1000, G4 pre-
189
filtration, HEPA-H14 final filtration, Q = 950 m³/h, Möcklinghoff Lufttechnik), which filter
190
airborne particles, were installed in laboratories for density separation, particle sorting and
191
FTIR analyses. All filtration steps were performed in a laminar flow cabinet (Scanlaf Fortuna,
192
Labogene), except for the ZnCl2 filtration by cartridge filter, to prevent airborne
193
contamination. All chemicals (e.g. FeSO4, H2O2) were filtered through polycarbonate filters
194
(0.2 µm pore size, Merck Millipore, IsoporeTM GTTP) to remove particulate contaminants
195
before usage. To remove contaminants from the MPSS it was filled with ZnCl2 and left to
196
settle for 5 h. The upper layer of the ZnCl2 solution (above the ball valve) was discarded prior
197
to the addition of the next sample. Cotton laboratory coats were generally worn to reduce
198
contamination from synthetic textiles. Latex gloves were worn for safety at work. To account
199
for possible process contaminations in the evaluation of the samples, a procedural blank was
200
run. For this purpose, an empty glass jar was rinsed with ZnCl2 into the MPSS instead of 10 ACS Paragon Plus Environment
Page 10 of 34
Page 11 of 34
Environmental Science & Technology
201
adding sediment and all the following procedures (filtration, purification and analysis) were
202
performed in the same way as for the other samples. The amounts of MPs determined in the
203
samples were blank-corrected by calculating the amount of MPs in 100 % of the sample
204
volume (volume of samples analyzed by µFITR: S3 = 1.99 %; HG-IV = 3.62 %; HG-V = 1.84
205
%; HG-VI = 2.29 %; HG-VII = 3.96 %; HG-VIII = 4.21 %; HG-IX = 67.7 %; N3 = 1.25 %; N5 =
206
1.85 %) and subtracting the amount of MPs determined in 100 % of the blank. The number of
207
particles kg-1 was calculated for each sample based on the amount of dry sediment.
208
Sea-ice concentration. To test for a correlation between the presence of sea ice
209
above the sample location and MP deposition, sea-ice concentration data were obtained by
210
the Centre for Satellite Exploitation and Research (CERSAT) at the Institut Français de
211
Recherche pour l’Exploitation de la Mer (IFREMER), France.39 The ice concentration was
212
calculated based on the ARTIST Sea Ice (ASI) algorithm developed at the University of
213
Bremen, Germany.40 Sea-ice concentration data from all HAUSGARTEN stations (Table 1)
214
were extracted for the summer months (May – July 2015) over an area of 12.5 × 12.5 km.
215
From this, the mean summer ice concentration and the days of sea ice coverage were
216
calculated for each station.
217
Data analysis. The MP counts of the large and small size fractions were combined
218
for data analyses. Since different sediment quantities were sampled from different stations
219
the data were converted to MP kg-1. In the current absence of established standards, MP
220
counts were additionally converted to MP L-1 and MP cm-2 to enable comparison with
221
published data given per unit volume and area although the latter may introduce variability
222
because of differences in the sample volumes used. The polymer composition and MP
223
particle size distribution of the different samples was compared by hierarchical cluster
224
analysis (PRIMER-e version 6.1.6) based on group average linkage of Bray-Curtis similarity
225
of square-root transformed polymer abundance data.41 Polymer diversity was computed
226
based on Shannon Wiener diversity (log base e). We tested for Pearson’s correlations
227
between chlorophyll a content (mean of the 5-cm sections) and MP quantity as well as
228
polymer diversity after establishing a normal distribution of the data using Anderson-Darling 11 ACS Paragon Plus Environment
Environmental Science & Technology
229
tests (Minitab 14; p > 0.05). Mean summer ice concentrations and number of days of sea ice
230
coverage were used for Spearman's rank correlation tests with MP quantities and diversity
231
for each station (Minitab 14).
232 233
RESULTS
234
Microplastic quantities. MPs were detected in all sediment samples with an overall
235
mean number of 4,356 (± 675 standard error) particles kg-1 sediment. The highest numbers
236
were found at the two northern stations N3 (6,595 MPs kg-1) and N5 (6,348 MPs kg-1),
237
followed by HG-V (5,568 MPs kg-1), HG-VIII (5,390 MPs kg-1), the southernmost station S3
238
(4,520 MPs kg-1), HG-IV (4,050 MPs kg-1), HG-VII (3,856 MPs kg-1), HG-VI (2,834 MPs kg-1)
239
and lastly by the deepest station HG-IX (42 MPs kg-1) (Figure 1; Table 2). It should be noted
240
that the MP counts from HG-IV and N3 may be slightly underestimated due to slight sample
241
loss during preparation. All results presented are blank corrected.
12 ACS Paragon Plus Environment
Page 12 of 34
Page 13 of 34
Environmental Science & Technology
242 243
Figure 1. Abundance and composition of microplastics detected in sediments from the Artic
244
deep sea (log scale, see Table 2 for abundance data).
245 246
Polymer composition. Eighteen different polymer types were identified in total from
247
all sediment samples (Table 2). In the larger size fraction (> 500 µm), 177 potential plastic
248
particles were analyzed, of which 31 were identified as plastic polymers (17.5 %). The 13 ACS Paragon Plus Environment
Environmental Science & Technology
249
remaining particles could not be identified as they had a hit quality below 700 except for one
250
cellulose particle and a particle identified as wild boar. While all plastics in this size fraction
251
were identified as polytetrafluoroethylene (PTFE), there was great variability in the polymer
252
composition in the small size fraction (< 500 µm) with 18 different types found in total ranging
253
between 5 (HG-IX) and 14 (HG-VIII) types per sample (Table 2). Since PTFE cannot be
254
detected within the spectral region of 3600 – 1250 cm-1 available for the particles < 500 µm in
255
µFTIR, no statement on the presence or absence of PTFE in the small size fraction can be
256
made. The polymer composition of the deepest station HG-IX, which was dominated by
257
polypropylene (Figure 2) and nitrile rubber shared only 11 % similarity with the other stations
258
(Figure S1). The southernmost station, S3, harbored a polymer composition, which was 63 %
259
similar to the remaining samples (Figure S1) and characterized by a great proportion (62 %)
260
of chlorinated polyethylene. The remaining samples had a 70 – 80 % similar polymer
261
composition (Figure S1). Polypropylene, nitrile rubber and PTFE occurred in all samples but
262
polyamide and chlorinated polyethylene were also detected in eight out of nine samples. In
263
terms of overall particle numbers from all stations, chlorinated polyethylene accounted for the
264
largest proportion (38 %), followed by polyamide (22 %), polypropylene (16 %) and nitrile
265
rubber (8 %) (Table 2). This is also reflected in the polymer composition from different
266
stations as summarized in Figure 1.
267
14 ACS Paragon Plus Environment
Page 14 of 34
Page 15 of 34
Environmental Science & Technology
268
Table 2. Microplastic abundance (number), diversity (Shannon-Winer H) and composition in sediments from different HAUSGARTEN stations. To
269
enable comparisons total MP kg-1 was converted to MP per area and volume. Polymer abundance in the samples refers to number kg-1 dry
270
sediment of the sample; polymer abundance in the blank refers to 100 % sample volume of the blank. All values are procedural blank corrected.*
271
slight sample loss. S3
Total MP abundance kg-1 MP abundance (>500 µm) kg-1 Total MP abundance cm-2 Total MP abundance L-1 Polymer diversity (H) Polyethylene chlorinated
HG-IV*
HG-V
HG-VI
HG-VII
HG-VIII
4520.22 4049.87 5568.02 2834.03 3855.99 5390.67
HG-IX
N3*
N5
41.76
6594.56
6348.27
Blank
Blank
(>500 µm)
( 5 mm (~22 %).42 Sediments collected at 15 locations along the densely populated
327
areas off the Belgium shelf (100 – 3,600 MPs kg−1)
328
3,146 MPs kg-1)
329
Lagoon in Italy (2,175 MPs kg-1) 45 and the Belgian coast (390 MPs kg-1).46 19
44
43
and the Dutch North Sea coast (54 -
approached more similar MP quantities as did sediments from the Venice
ACS Paragon Plus Environment
Environmental Science & Technology
Page 20 of 34
330
Still, overall the abundance of MP in the deep Fram Strait appears to be higher than
331
in all other benthic regions investigated. Some of the observed differences may be due to
332
differences in the methodology used. Unlike coring devices, for example, grabs produce a
333
bow wave when lowered to the seafloor, which flushes the top sediment layer aside
334
preventing the detection of recently deposited pollutants. In addition, the MPSS recovers
335
significantly more MP compared with other separation methods, especially in the small size
336
range.37 All of the above studies relied on the analysis of visually pre-selected particles. Our
337
data showed, however, that nearly 80 % of the MPs were smaller than 25 µm. This
338
significant proportion would have gone unnoticed leading to serious underestimates. Despite
339
these methodological differences the high abundance of microplastics in the deep-sea
340
sediments of the remote Arctic Ocean is striking.
48
341
Still, even if a more sensitive methodological approach allowed us to detect higher
342
MP quantities the magnitude of the differences indicates that HAUSGARTEN may be in or
343
close to a plastic accumulation area. Similar MP numbers were recorded near the sea
344
surface southwest of Svalbard using an underway sampling device and visual pre-selection
345
(21 converted: 2,680 MP L-1). Recently, high numbers of small plastic debris were also
346
reported from the sea surface in the Fram Strait pointing to an accumulation area south of
347
HAUSGARTEN.17 It was suggested that a significant fraction of this debris likely originated
348
from Northern Europe and was transported to the North with the Thermohaline Circulation.
349
Still, inputs from local sources may increasingly also contribute to this since anthropogenic
350
activities such as fisheries and tourism have increased markedly due to the receding sea
351
ice.19 Plastic debris from fisheries nowadays dominates on the beaches of Svalbard.47 The
352
release of MP entrained in Arctic sea ice during melting processes
353
considered another reason for the high MP quantities recorded although this has to be
354
verified, for example, by analysis of samples from year round moored particle traps.48
355
Differences
between
HAUSGARTEN
stations.
22
The
in the region can be
two
northernmost
356
HAUSGARTEN stations N3 and N5 contained the highest MP numbers. Both stations are
357
located within or close to the marginal ice zone, as shown by the highest ice concentration 20 ACS Paragon Plus Environment
Page 21 of 34
Environmental Science & Technology
358
and duration of sea ice coverage. Arctic sea ice entrains enormous quantities of MP 22 during
359
ice formation in the Central Arctic and may act as transport vehicle: after the ice breaks up in
360
the Central Arctic in spring it is transported to the south as ice floes with the Transpolar Drift.
361
On route, it encounters warmer Atlantic surface waters and continues to melt possibly
362
releasing entrained MPs. Depending on the sinking velocity, there may be some horizontal
363
displacement of particles from their point of origin at the sea surface as they descend to the
364
seafloor. However,
365
catchment areas. Increasing numbers of small plastic fragments (< 10 cm) were also
366
recorded on seafloor photographs at N3.19 The number of MP at the two northern stations
367
may thus be higher because they receive MP from meltwater as well as distant sources
368
through the Thermohaline Circulation.
49
reported fast sinking rates for some MP implying reasonably small
369
The other HAUSGARTEN stations may harbor a lower MP load because they receive
370
MPs primarily only through the Thermohaline Circulation, whereas the northern stations are
371
affected by both Atlantic waters and meltwater carrying MPs. The positive correlation
372
between MP levels and chlorophyll a content suggests that Algae play a role in the
373
downward transport. It should be noted that there was no significant correlation with total
374
phytodetrital input, which also includes phaeophytin, an indicator of refractory material. This
375
highlights the potential role of freshly deposited algal rather than older material. Indeed, the
376
vertical transport of originally positively buoyant MPs may be accelerated significantly by the
377
presence of aggregating Algae.50, 51 In the study area, the ice algal diatom Melosira arctica
378
forms dense aggregates beneath the sea ice. During melting, such aggregates may entrain
379
MP and rush to the deep seafloor
380
waters carry increasing amounts of the colony forming algae Phaeocystis pouchetii to
381
HAUSGARTEN 27, 48 whose polysaccharide gel matrix may entrain buoyant MP, too.
52
facilitating the deposition of MPs. In addition, Atlantic
382
The low quantities of MP in the Molloy Deep, the deepest depression of the Arctic,
383
were surprising. If nothing else, higher MP levels were expected because of the funnel-
384
shaped surrounding topography and the presence of downwards directed eddy systems, all
385
favouring the accumulation of MPs. It could be argued that MP export is attenuated with 21 ACS Paragon Plus Environment
Environmental Science & Technology
Page 22 of 34
386
depth as is the vertical export of particulate organic matter.53 However, the third highest MP
387
concentration recorded at the nearby station HG-VIII at similar depth (5,100 m, 12 km
388
distance) contradicts this notion. Another possibility is that MPs have evaded our detection
389
because they were already incorporated in an exceptionally high standing stock of infaunal
390
meiofauna
391
primarily of the deposit-feeding sea cucumber Elpidia heckeri.55 Recently, epibenthic
392
megafauna including sea cucumbers from the deep SW Indian Ocean and equatorial mid-
393
Atlantic were shown to ingest MP.56 Microplastic abundance in North Sea and English
394
Channel sediments was influenced by other factors including carbon content and grain size.44
395
By contrast, at HAUSGARTEN, neither organic carbon content nor porosity appeared to be
396
correlated with MP numbers. Of the parameters tested, only chlorophyll a and marginally
397
possibly also summer sea-ice concentration appeared to be correlated although low sample
398
sizes may have obscured possible correlations. As stated above, this could be seen as an
399
indication of enhanced vertical transport via incorporation in fast-sinking ice-algal
400
aggregates. Still, samples from the water column or experimental work are required to
401
establish mechanistic links. In addition, further benthic studies are needed to assess if the
402
wider Arctic region is contaminated with MP or if the Fram Strait area is an accumulation
403
zone.
54
and epibenthic megafauna, which distinguishes this station and consists
404
Particle composition. Polypropylene, nitrile rubber and PTFE occurred in all
405
samples but polyamide and chlorinated polyethylene were also detected in eight out of nine
406
samples. In terms of overall particle numbers from all stations, chlorinated polyethylene
407
accounted for the largest proportion (38 %), followed by polyamide (22 %), polypropylene
408
(16 %) and nitrile rubber (8 %). Since the density of PTFE (2.10 – 2.30 g cm-3),
409
rubber (1.3 g cm-3) and polyamide (1.13 g cm-3) exceeds the density of sea water (1.02 – 1.03
410
g cm-3)
411
chlorinated polyethylene have a lower density
412
including eddies and wind mixing,58 biofouling, incorporation in sinking aggregates and
413
vertical transport with biota or faeces must counteract their buoyancy. Polypropylene and
4
57
nitrile
these MPs are likely to sink to the seafloor directly. By contrast, polypropylene and 4
such that a combination of processes
22 ACS Paragon Plus Environment
Page 23 of 34
Environmental Science & Technology
59
414
polyethylene are the most widely demanded plastic types in Europe
415
e.g. packaging and fishing gear.4 Therefore, its prevalence does not come as a surprise.
416
These two polymer types accounted also for almost half of the MPs from Atlantic surface
417
waters.57 Microplastics from surface waters southwest of Svalbard contained polyester (15
418
%), polyamide (15 %), acrylic (10 %), polyethylene (5 %) and polyvinyl chloride (5 %).21
419
Polyethylene and to a lesser degree also polyamide dominated MP in Arctic sea ice sampled
420
in 2014, one year before our sediment sampling, especially in the two cores from the Fram
421
Strait (Peeken, unpubl. data). All polymers detected in the ice cores or surfaces waters of the
422
Arctic Ocean (except acrylic) have been also detected in the deep-sea sediments of the
423
Arctic Ocean. This indicates that both surface waters and sea ice are possible sources of MP
424
found in the sediment at HAUSGARTEN. Only few previous studies analyzed the
425
composition of the polymers identified. Polyester followed by acrylic fibers dominated in
426
sediments from the deep NE Atlantic, Mediterranean, SW Indian Ocean samples and
427
subarctic sites.25 Central Arctic ice cores were also characterized by a different MP
428
composition, which was dominated by polyester (21 %) and nylon/polyamide (16 %),
429
polypropylene (3 %), and then by 2 % each of polystyrene, acrylic, and polyethylene.22 Still,
430
the majority of particles were fibers, which were not considered in the present study. Other
431
studies on MP in the deep sea did not describe the polymer composition.23, 24 Unfortunately,
432
the abundance of coal particles could not be determined but such particles were also
433
reported before in deep-sea sediments between New Zealand and Antarctica (5,314 m
434
depth) and the Porcupine Abyssal Plain (4,100 m depth)
435
Subarctic Ocean.61 The latter was attributed to atmospheric deposition and fluvial discharge,
436
as ice-rafted material, coastal erosion, and the adsorption of dissolved black carbon onto
437
particles.
60
and widely used for
as well as from the Arctic and
438
Polymer Size. Overall, 83 % of the analyzed particles in the large size fraction (> 500
439
µm) were not identified as polymers. This highlights once more a likely overestimation of MP
440
particles when relying exclusively on visual identification.37 At the same time, it cannot be
23 ACS Paragon Plus Environment
Environmental Science & Technology
Page 24 of 34
441
excluded that some particles may be overlooked during the visual identification step leading
442
to an underestimation.
443
The analysis of the particles in the large size fraction showed also differences
444
compared to others studies reporting particles > 500 µm. While other studies detected
445
particles with striking colors as well as white, black, grey and translucent particles
446
PTFE particles were identified in this study that were white, black or grey. By contrast,
447
particles of a striking color were not identified as polymers showing once again the need for
448
spectroscopic methods for a reliable identification of polymers.
62, 63
only
449
As stated above, some 80 % of the MPs were ≤ 25 µm. The size structure of MP
450
particles was steadily increasing in numbers towards lower sizes with no sign of saturation
451
towards the lower size end. This may indicate that deep-sea sediments contain even more
452
particles in yet smaller particle sizes, which have evaded our detection and that of previous
453
studies. In Atlantic surface waters, the majority of MP particles (64 %) detected were
100 µm) are translocated to organs of the tropical fiddler crab
574
Uca rapax. Mar. Pollut. Bull. 2015, 96, 491-495.
575 576
(14) Farrell, P.; Nelson, K., Trophic level transfer of microplastic: Mytilus edulis (L.) to Carcinus maenas (L.). Environ. Pollut. 2013, 177, 1-3.
577
(15) Moore, C. J.; Moore, S. L.; Leecaster, M. K.; Weisberg, S. B., A comparison of plastic
578
and plankton in the North Pacific Central Gyre. Mar. Pollut. Bull. 2001, 42, (12), 1297-1300. 28 ACS Paragon Plus Environment
Page 28 of 34
Page 29 of 34
Environmental Science & Technology
579
(16) van Sebille, E.; England, M. H.; Froyland, G., Origin, dynamics and evolution of
580
ocean garbage patches from observed surface drifters. Environ. Res. Lett. 2012, 7, (4),
581
044040.
582
(17) Cózar, A.; Martí, E.; Duarte, C. M.; García-de-Lomas, J.; van Sebille, E.; Ballatore, T.
583
J.; Eguíluz, V. M.; González-Gordillo, J. I.; Pedrotti, M. L.; Echevarría, F.; Troublè, R.;
584
Irigoien, X., The Arctic Ocean as a dead end for floating plastics in the North Atlantic branch
585
of the Thermohaline Circulation. Sci. Adv. 2017, 3, (e1600582).
586 587
(18) Bergmann, M.; Klages, M., Increase of litter at the Arctic deep-sea observatory HAUSGARTEN. Mar. Pollut. Bull. 2012, 64, 2734–2741.
588
(19) Tekman, M. B.; Krumpen, T.; Bergmann, M., Marine litter on deep Arctic seafloor
589
continues to increase and spreads to the North at the HAUSGARTEN observatory. Deep-
590
Sea Res. Pt.1 2017, 120, 88-99.
591
(20) Bergmann, M.; Sandhop, N.; Schewe, I.; D’Hert, D., Observations of floating
592
anthropogenic litter in the Barents Sea and Fram Strait, Arctic. Polar Biol. 2015, 39, (3),
593
553-560.
594
(21) Lusher, A. L.; Tirelli, V.; O’Connor, I.; Officer, R., Microplastics in Arctic polar waters:
595
the first reported values of particles in surface and sub-surface samples. Sci. Rep. 2015, 5,
596
14947.
597
(22) Obbard, R. W.; Sadri, S.; Wong, Y. Q.; Khitun, A. A.; Baker, I.; Thompson, R. C.,
598
Global warming releases microplastic legacy frozen in Arctic Sea ice. Earth's Future 2014,
599
2, (6), 2014EF000240.
600 601 602 603
(23) van Cauwenberghe, L.; Vanreusel, A.; Mees, J.; Janssen, C. R., Microplastic pollution in deep-sea sediments. Environ. Pollut. 2013, 182, 495-499. (24) Fischer, V.; Elsner, N. O.; Brenke, N.; Schwabe, E.; Brandt, A., Plastic pollution of the Kuril-Kamchatka-trench area (NW Pacific). Deep-Sea Res. Pt. 2 2015, 111, 399-405.
604
(25) Woodall, L. C.; Sanchez-Vidal, A.; Canals, M.; Paterson, G. L. J.; Coppock, R.;
605
Sleight, V.; Calafat, A., M.; Rogers, A. D.; Narayanaswamy, B. E.; Thompson, R. C., The
606
deep sea is a major sink for microplastic debris. R. Soc. Open Sci. 2014, 1, (4), 140317. 29 ACS Paragon Plus Environment
Environmental Science & Technology
607
(26) Tagg, A. S.; Harrison, J. P.; Ju-Nam, Y.; Sapp, M.; Bradley, E. L.; Sinclair, C. J.;
608
Ojeda, J. J., Fenton's reagent for the rapid and efficient isolation of microplastics from
609
wastewater. Chem. Commun. 2017, 53, (2), 372-375.
610
(27) Soltwedel, T.; Bauerfeind, E.; Bergmann, M.; Bracher, A.; Budaeva, N.; Busch, K.;
611
Cherkasheva, A.; Fahl, K.; Grzelak, K.; Hasemann, C.; Jacob, M.; Kraft, A.; Lalande, C.;
612
Metfies, K.; Nöthig, E.-M.; Meyer, K.; Quéric, N.-V.; Schewe, I.; Włodarska-Kowalczuk, M.;
613
Klages, M., Natural variability or anthropogenically-induced variation? Insights from 15
614
years of multidisciplinary observations at the arctic marine LTER site HAUSGARTEN. Ecol.
615
Indic. 2016, 65, 89–102.
616
(28) Beszczynska-Möller, A.; Fahrbach, E.; Schauer, U.; Hansen, E., Variability in Atlantic
617
water temperature and transport at the entrance to the Arctic Ocean, 1997–2010. ICES J.
618
Mar. Sci. 2012, 69, (5), 852-863.
619 620
(29) Thiel, H., Benthos in upwelling regions. In Upwelling ecosystems; Boje, R.; Tomczak, M., Eds; Springer: Berlin, Germany, 1978; pp 124-138.
621
30. Yentsch, C. S.; Menzel, D. W., A method for the determination of phytoplankton
622
chlorophyll and phaeophytin by fluorescence. Deep-Sea Res. Oceanogr. Abstr. 1963, 10,
623
(3), 221-231.
624 625
(31) Holm-Hansen, O.; Lorenzen, C. J.; Holmes, R. W.; Strickland, J. D. H., Fluorometric determination of chlorophyll. J. Cons. Int. Explor. Mer 1965, 30, (1), 3-15.
626
(32) Imhof, H. K.; Schmid, J.; Niessner, R.; Ivleva, N. P.; Laforsch, C., A novel, highly
627
efficient method for the separation and quantification of plastic particles in sediments of
628
aquatic environments. Limnol. Oceanogr. Methods 2012, 10, (7), 524-537.
629
(33) Norén, F.; Naustvoll, L.-J. Survey of microscopic anthropogenic particles in
630
Skagerrak; TA 2779–2011; Klima- og forurensningsdirektoratet TA: Lysekil and Flødevigen,
631
Sweden; 2011; pp 1-20.
632
(34) Mintenig, S. M.; Int-Veen, I.; Löder, M. G. J.; Primpke, S.; Gerdts, G., Identification of
633
microplastic in effluents of waste water treatment plants using focal plane array-based
634
micro-Fourier-transform infrared imaging. Water Res. 2017, 108, 365-372. 30 ACS Paragon Plus Environment
Page 30 of 34
Page 31 of 34
Environmental Science & Technology
635
(35) Claessens, M.; van Cauwenberghe, L.; Vandegehuchte, M. B.; Janssen, C. R., New
636
techniques for the detection of microplastics in sediments and field collected organisms.
637
Mar. Pollut. Bull. 2013, 70, (1-2), 227-233.
638
(36) Tagg, A. S.; Sapp, M.; Harrison, J. P.; Ojeda, J. J., Identification and quantification of
639
microplastics in wastewater using focal plane array-based reflectance micro-FT-IR imaging.
640
Anal. Chem. 2015, 87, (12), 6032-6040.
641
(37) Löder, M. G. J.; Gerdts, G., Methodology used for the detection and identification of
642
microplastics – a critical appraisal. In Marine Anthropogenic Litter; Bergmann, M.; Gutow,
643
L.; Klages, M., Eds; Springer: Berlin, Germany, 2015; pp 201-227.
644
(38) Primpke, S.; Lorenz, C.; Rascher-Friesenhausen, R.; Gerdts, G., An automated
645
approach for microplastics analysis using focal plane array (FPA) FTIR microscopy and
646
image analysis. Anal. Methods 2017, 9, (9), 1499-1511.
647
(39) Ezraty, R.; Girard-Ardhuin, F.; Pioll, J. F.; Kaleschke, L.; Heygster, G., Arctic and
648
Antarctic Sea Ice Concentration and Arctic Sea Ice Drift Estimated from Special Sensor
649
Microwave Imager Data. 2007.
650 651 652 653
(40) Spreen, G.; Kaleschke, L.; Heygster, G., Sea Ice Remote Sensing Using AMSR-E 89 GHz Channels. J. Geophys. Res. 2008, 113, 1-14. (41) Clarke, K. R.; Gorley, R. N., Primer v6: User Manual / Tutorial. Plymouth, UK, 2006; p 190.
654
(42) Munari, C.; Corbau, C.; Simeoni, U.; Mistri, M., Marine litter on Mediterranean shores:
655
Analysis of composition, spatial distribution and sources in north-western Adriatic beaches.
656
Waste Manage. 2016, 49, 483-490.
657
(43) Leslie, H. A.; Brandsma, S. H.; van Velzen, M. J. M.; Vethaak, A. D., Microplastics en
658
route: Field measurements in the Dutch river delta and Amsterdam canals, wastewater
659
treatment plants, North Sea sediments and biota. Environ. Int. 2017, 101, 133–142.
660
(44) Maes, T.; van der Meulen, M. D.; Devriese, L. I.; Leslie, H. A.; Huvet, A.; Frère, L.;
661
Robbens, J.; Vethaak, A. D., Microplastics Baseline Surveys at the Water Surface and in
662
Sediments of the North-East Atlantic. Front. Mar. Sci. 2017, 4, (135), 1-13. 31 ACS Paragon Plus Environment
Environmental Science & Technology
663
(45) Vianello, A.; Boldrin, A.; Guerriero, P.; Moschino, V.; Rella, R.; Sturaro, A.; Da Ros,
664
L., Microplastic particles in sediments of Lagoon of Venice, Italy: first observations on
665
occurrence, spatial patterns and identification. Estuar. Coast. Shelf Sci. 2013, 130, 54-61.
666
(46) Claessens, M.; Meester, S. D.; Landuyt, L. V.; Clerck, K. D.; Janssen, C. R.,
667
Occurrence and distribution of microplastics in marine sediments along the Belgian coast.
668
Mar. Pollut. Bull. 2011, 62, (10), 2199-2204.
669 670
(47) Bergmann, M.; Lutz, B.; Tekman, M. B.; Gutow, L., Citizen scientists reveal: marine litter pollutes Arctic beaches and affects Arctic wildlife. Mar. Pollut. Bull. under review.
671
(48) Lalande, C.; Bauerfeind, E.; Nöthig, E.-M., Downward particulate organic carbon
672
export at high temporal resolution in the eastern Fram Strait: influence of Atlantic Water on
673
flux composition. Mar. Ecol. Prog. Ser. 2011, 440, 127-136.
674 675
(49) Khatmullina, L.; Isachenko, I., Settling velocity of microplastic particles of regular shapes. Mar. Pollut. Bull. 2017, 114, (2), 871-880.
676
(50) Long, M.; Moriceau, B.; Gallinari, M.; Lambert, C.; Huvet, A.; Raffray, J.; Soudant, P.,
677
Interactions between microplastics and phytoplankton aggregates: Impact on their
678
respective fates. Mar. Chem. 2015, 175, 39-46.
679
(51) Long, M.; Paul-Pont, I.; Hégaret, H.; Moriceau, B.; Lambert, C.; Huvet, A.; Soudant,
680
P., Interactions between polystyrene microplastics and marine phytoplankton lead to
681
species-specific hetero-aggregation. Environ. Pollut. 2017, 228, 454-463.
682
(52) Boetius, A.; Albrecht, S.; Bakker, K.; Bienhold, C.; Felden, J.; Fernández-Méndez, M.;
683
Hendricks, S.; Katlein, C.; Lalande, C.; Krumpen, T.; Nicolaus, M.; Peeken, I.; Rabe, B.;
684
Rogacheva, A.; Rybakova, E.; Somavilla, R.; Wenzhöfer, F., Export of algal biomass from
685
the melting arctic sea ice. Science 2013, 339, (6126), 1430-1432.
686 687 688 689
(53) Suess, E., Particulate organic carbon flux in the oceans-surface productivity and oxygen utilization. Nature 1980, 288, (5788), 260-263. (54) Soltwedel, T.; Miljutina, M.; Mokievsky, V.; Vopel, K., The meiobenthos of the Molloy Deep (5600 m), Fram Strait, Arctic Ocean. Vie Milieu 2003, 53, 1-13.
32 ACS Paragon Plus Environment
Page 32 of 34
Page 33 of 34
Environmental Science & Technology
690
(55) Soltwedel, T.; Jaeckisch, N.; Ritter, N.; Hasemann, C.; Bergmann, M.; Klages, M.,
691
Bathymetric patterns of megafaunal assemblages from the arctic deep-sea observatory
692
HAUSGARTEN. Deep-Sea Res. Pt. 1 2009, 56, (10), 1856-1872.
693 694
(56) Taylor, M. L.; Gwinnett, C.; Robinson, L. F.; Woodall, L. C., Plastic microfibre ingestion by deep-sea organisms. Sci. Rep. 2016, 6, 33997.
695
(57) Enders, K.; Lenz, R.; Stedmon, C. A.; Nielsen, T. G., Abundance, size and polymer
696
composition of marine microplastics ≥ 10 µm in the Atlantic Ocean and their modelled
697
vertical distribution. Mar. Pollut. Bull. 2015, 100, (1), 70-81.
698
(58) Kukulka, T.; Proskurowski, G.; Morét-Ferguson, S.; Meyer, D. W.; Law, K. L., The
699
effect of wind mixing on the vertical distribution of buoyant plastic debris. Geophys. Res.
700
Lett. 2012, 39, (7), L07601.
701
(59) PlasticsEurope Plastics-the Facts 2016; Brussels, 2016.
702
(60) Masiello, C. A.; Druffel, E. R. M., Black Carbon in Deep-Sea Sediments. Science
703
1998, 280, (5371), 1911-1913.
704
(61) Fang, Z.; Yang, W.; Chen, M.; Zheng, M.; Hu, W., Abundance and sinking of
705
particulate black carbon in the western Arctic and Subarctic Oceans. Sci. Rep. 2016, 6,
706
29959.
707 708 709 710 711 712
(62) Stolte, A.; Forster, S.; Gerdts, G.; Schubert, H., Microplastic concentrations in beach sediments along the German Baltic coast. Mar. Pollut. Bull. 2015, 99, (1-2), 216-229. (63) Shaw, D. G.; Day, R. H., Colour- and form-dependent loss of plastic micro-debris from the North Pacific Ocean. Mar. Pollut. Bull. 1994, 28, (1), 39-43. (64) Fazey, F. M. C.; Ryan, P. G., Biofouling on buoyant marine plastics: An experimental study into the effect of size on surface longevity. Environ. Pollut. 2016, 210, 354-360.
713
(65) Oliveros, E.; Legrini, O.; Hohl, M.; Müller, T.; Braun, A. M., Industrial waste water
714
treatment: large scale development of a light-enhanced Fenton reaction. Chem. Eng.
715
Process. 1997, 36, (5), 397-405.
33 ACS Paragon Plus Environment
Environmental Science & Technology
716
(66) Löder, M. G. J.; Kuczera, M.; Mintenig, S.; Lorenz, C.; Gerdts, G., Focal plane array
717
detector-based micro-Fourier-transform infrared imaging for the analysis of microplastics in
718
environmental samples. Env. Chem. 2015, 12, 563-581.
34 ACS Paragon Plus Environment
Page 34 of 34